Fluorocarbon triazine compounds



United States Patent FLUOROCARBON TRIAZINE COMPOUNDS Yung Ki Kim andOgden R. Pierce, Midland, Mich., as-

signors to Dow Corning Corporation, Midland, Mich., a corporation ofMichigan No Drawing. Filed June 3, 1968, Ser. No. 733,833 Int. Cl. C07d55/12 US. Cl. 260--248 2 Claims ABSTRACT OF THE DISCLOSURE The inventionprovides triazines of the formula in which R, is a monovalentpolyfluorinated hydrocarbon radical of no more than 12 carbon atoms andn has a value of from 1 to 10 inclusive. Fluoroalkylenetriazinescontaining silanes, silanols and siloxanes are disclosed as fluids,resins and elastomers.

In one aspect the invention relates to vinyl perfluorocarbon triazines.In another aspect the invention relates to polyfluorinated hydrocarbontriazine-containing silanes and silanols. Further, the invention relatesto siloxane polymers containing triazine groups.

According to the invention, there are provided triazine compounds of theformula:

om=on o Fan-o where R: is a monovalent polyfiuorinated hydrocarbonradical of no more than 12 carbon atoms and n has a value of from 1 to10 inclusive.

R can be any suitable monovalent fluorohydrocarbon radical, such as,perfluoroalkyl, for example, trifluoro methyl, iso(heptafiuoropropyl),perfluoroisobutyl, perfluorooctyl or perfluorodecyl; unsaturatedfluorocarbon radicals, for example, pentafluoroallyl and4-perfluorohexenyl; perfluorocycloaliphatic radicals such asperfiuorocyclohexyl, perfluorocyclopentyl and perfiuorocyclohexenyl; orany aryl-containing radical, for example, pentafluorophenyl,nonafluoroxenyl, heptafluorotolyl, heptafluoronaphthyl,heptafluorobenzyl or MperfiuorophenyDperfluoroethyl. Also included aremonovalent hydrocarbon radicals partially substituted with fluorine suchas trifiuoroethyl and 3,3,3-trifluoropropyl and radicals containingbromine or chlorine such as bromodifluoromethyl, chlorodifiuoromethyland chlorodifluoroethyl.

R is preferably trifluoromethyl, bromodifiuoromethyl, trifiuoroethyl orother fluoroalkyl radicals. The presence of small amounts offiuoroolefinic radicals provides crosslinking sites in polymers of theabove-described triazines.

The triazines of the invention can be prepared by the ammonolysis ofvinyl perfluorocarbon nitriles to obtain the corresponding amidinefollowed by acylation and ring closure utilizing a fluorocarbon acidanhydride to give the divinyl perfluorocarbon triazine structure. Thereaction is as follows:

2CHr=CH(O 2):-CEN NHa Ammonolysis is carried out at low temperatures,for example, C., while the acylation proceeds at higher temperatures (0to +40 C.) in the presence of excess anhydride.

The preparation of the alpha-vinyl, omega-nitrile perfluoroalkane isaccomplished by reacting ethylene with an omega-bromoperfluoroester,Br(CF COOR, in the presence of free radical catalysts, such asperoxides. The reaction is conveniently carried out at a temperaturefrom to C. under 25 to 50 p.s.i. pressure. The prodnot from the additionof one ethylene group to the ester is dehydrohalogenated by reactionWith an alkali metal alkoxide in alcohol solvent. In carrying out thereaction, the alkoxide of the alcohol corresponding to the R group inthe ester is employed and the same alcohol should be used as thesolvent.

The nitrile is prepared by conventional reactions from the ester. Theester is hydrolyzed to the acid which is then ammonolyzed to produce theamide,

CH CH(CF CONH The amide can be dehydrated by conventional dehydratingagents, such as P 0 or phosphorous pentachloride to obtain CH =CH(CFCEN. This reaction is described in detail in my copending applicationSer. No. 598,604, filed Dec. 2, 1966.

Examples of the triazine compounds of the invention include thefollowing:

and

The divinyltriazine compounds of the invention are heat stable fluidsand can be utilized as heat transfer media, hydraulic fluids anddielectric fluids.

Further in accordance with the invention, there are providedorganosilane and organosilanol compounds of the formula:

. XmS1CHzCHg(CFz)nC G(CFz)nCH2CH2S1Xm a, r l a, la

Where X is a hydrogen atom, the hydroxy group or a hydrolyzable group, Ris a monovalent hydrocarbon radical or a ACH CH radical in Which A is aperfluoroalkyl radical, R is as defined hereinbefore, n has a value offrom 1 to 10 inclusive, m has a value of t0 3 inclusive.

The term hydrolyzable group means that the group is removed from the Siatom by reaction with water at room temperature. As described above, Xcan be any hydrolyzable group such as halogen atoms; such as fluorine,chlorine or bromine; hydrocarbonoxy groups such as methoxy, ethoxy,octadecyloxy, allyloxy, cyclohexyloxy, phenoxy, tolyloxy, benzyloxy,

acyloxy groups such as acetoxy, propionyloxy, benzoyloxy,cyclohexoyloxy, and

ketoxime groups such as amine groups such as sulfide groups such as somand s--@ the nitrile groups, the isocyanate group, sulfate groups suchas o sulfonate groups such as carbamate groups such as OOCNHCH OOCN(CHand OOCN(C H and groups such as ON(CH and ON(C H- R can be anymonovalent hydrocarbon radical such as alkyl radicals such as methyl,ethyl, isopropyl, t-butyl,

octadecyl or myricyl; cycloaliphatic radicals such as cyclohexyl,cyclopentyl and cyclohexenyl; aromatic hydrocarbon radicals such asphenyl, tolyl, xenyl, naphthyl and xylyl; aralkyl hydrocarbon radicalssuch as benzyl, beta-phenylethyl and beta-phenylpropyl; and alkenylradicals such as vinyl, allyl, hexenyl, butadienyl or other unsaturatedgroups including CHEC-.

R can also be any radical of the formula ACH CH in Which A is aperfluoroalkyl radical such as The above described organosilanes andsilanols (II) are best prepared by reacting silanes of the formula withthe previously described triazines of the Formula I I Rf This reactionis carried out in the presence of an excess of platinum catalyst, suchas chloroplatinic acid, in the conventional manner for adding SiHcompounds to compounds having the terminal CH =CH group.

The silanols of the invention (i.e. Where X is OH) can be prepared byhydrolyzing the corresponding hydrolyzable silane under neutralconditions by any of the well-known methods such as hydrolysis of thosecompounds in Which X is methoxy.

When R is an alkenyl radical in the silane of the invention, the R groupis added to the Si atom by reaction with a Grignard reagent, RMgX, afterthe vinyl addition reaction.

Examples of the above defined compositions include:

Thirdly, the invention provides siloxanes having at least one unit ofthe formula in which R, R; and n are as described before and each aindependently has a value of from 0 to 2 inclusive, any remaining unitsin the siloxane being of the formula ZbSlO T in which Z is a hydrocarbonor halohydrocarbon radical, or X group and b has a value of from 0 to 3inclusive.

The siloxanes of the invention can be prepared by two methods. First isby the hydrolysis or cohydrolysis of the above defined silanes (II), byconventional means, or by cohydrolysis of the defined silanes (II) withsilanes of the formula Z SiX in which Z, X and b are as defined above.The particular method chosen for hydrolysis or cohydrolysis can varydepending upon the nature of the substituent groups on the silicon.There are no critical conditions other than those for hydrolyzing andcohydrolyzing silanes.

The second method of preparing such siloxanes is by the addition ofsiloxanes containing Sil-I groups to the divinyl triazines (I) of theinvention in the presence of platinum catalysts. The conditions forcarrying out this reaction are those normally employed for the additionof SiH-containing siloxanes to olefins.

As can be seen, the siloxanes of the invention can be homopolymers orcopolymers of various types of triazinecontaining siloxane units. Inaddition, the siloxanes can contain siloxane units of the formula ZbSiOT in which b has a value of from 0 to 3 inclusive. Thus, included areunits of the type SiO ZSiO Z SiO and Z SiO Z can be a hydrogen atom, anyof the above defined X groups or any hydrocarbon radical, such as themonovalent radicals specifically shown for R; divalent hydrocarbonradicals such as alkylene radicals, for example, methylene, dimethylene,trimethylene or tetramethylene; arylene radicals, for example,phenylene, xenylene, tolylene, xylylene or naphthylene; cycloalkyleneradicals, for example, cyclohexylene and cyclopentylene; and alkenylradicals, for example, vinyl, allyl, hexenyl and butadienyl.

Z can also be any halohydrocarbon radical such as chloromethyl, gammachloropropyl, brorno octadecyl, chlorocyclohexyl, bromocyclohexenyl,3-chlorobutenyl-4, chlorophenyl, bromoxenyl, 4,4,4 trifluorooctyl,tetrachlorophenyl, p-chlorobenzyl, 3,3,3-trifluoropropyl and C F CH CHThe siloxanes of the invention are fluids, resins and elastomers. Theelastomers are especially useful as sealants where a wide range oftemperature stability and chemical inertness are required.

The following examples are illustrative of the compositions of theinvention and should not be construed as unduly limiting the invention,which is properly delineated in the appended claims.

EXAMPLE 1 A mixture of 162.0 g. (1.06 moles) of CH =CHCF CF CN and 9.4g. (0.55 mole) of dry ammonia in 250 ml. of dry methylene chloride wasstirred slowly at room temperature for 8 hours under a coolingcondenser. The reaction mixture was kept at room temperature for 36hours without stirring and was then added slowly into a stirred mix- 6ture of 290.0 g. (1.38 moles) of trifluoroacetic anhydride and 400 ml.of dry methylene chloride at: 0 to 5 C. This mixture was kept atroom-temperature for 18 hours and then poured into twice its volume ofice cold water. The methylene chloride layer was separated, washed withwater, and dried over Drierite.

After evaporation of methylene chloride, the resulting product wasdistilled to yield 160.0 g. (72.8% yield) of the pure divinyltriazine,B.P. 110 to 111 C. (22 mm.), 11 1.3785. The molecular Weight by massspectroscopy was found to be 401 (cal. 401). The elemental analysis, Fand H resonance, and infrared spectral properties showed the structureto be EXAMPLE 2 Into a stirred mixture of g. (0.223 mole) of and 157 g.(0.892 mole) of 3,3,3-trifluoropropylrnethylchlorosilane was added 4.2ml. of 0.1 M solution of chloroplatinic acid in isopropyl alcohol. Themixture was heated while stirring under reflux. At end of 16 hours ofreflux an additional 2.5 ml. of 0.1 M solution of chloroplatinic acid inisopropyl alcohol was introduced, and the reaction mixture wascontinuously heated under reflux for a total of 87 hours. The excess3,3,3-trifluoropropylmethylchlorosilane and volatile materials werestripped off in vacuo at room-temperature. The resulting crude product(148 g.) was fractionated to yield n 1.4050. The elemental analysis andspectral properties (F and H N.M.R. and LR.) were consistent with thediadduct.

EXAMPLE 3 Utilizing the method of Example 2, about 16 hours of reflux ofa solution of N CHZ=CHCFZCF2C CCF2CF2CH=CH2 (1.5 g., 0.0037 mole),3,3,3-trifluoropropylmethylchlorosilane (2.0 g., 0.011 mole), and 50,ul. of 0.1 M solution of chloroplatinic acid in isopropyl alcohol gave45% yield of CH3 N CH3 7 EXAMPLE 4 About 29 hours of gamma-irradiation(1.6 mrad. per hour at 160 C.) of a solution containing 5.0 g. (0.013mole) of and 7.6 g. (0.043 mole) of3,3,3-trifiuoropropylmethylchlorosilane gave was obtained. The molecularweight by the vapor phase osmometry was found to be 795 (calcd. 717),and the hydroxy content was found to be 4.52% (calcd. 4.74%). Thespectral data were in agreement with the diol structure.

and 5 drops of tetramethylguanidine-trifluoroacetic acid solution washeated while mixing by rotation at to C. under -15 mm. Hg for 27 hours,at C. under 0.3 mm. Hg for 16 hours, and then at C. under 0.2 mm. Hg for45 minutes. The resulting polymer was 17.5 g. of rubbery gum having thestructure shown below:

The polymerization catalyst (tetramethylguanidinetrifluoroacetic acidsolution) was removed from the rubbery polymer in the following manner:The polymer was dissolved in isopropyl acetate, treated with acidicsynthetic resin, washed with water, and dried over Drierite. Evaporationof isopropyl acetate gave the catalyst-free rubbery gum.

EXAMPLE 7 A mixture of 25.0 g. (0.0624 mole) of N CHz=CHCFzCF -(|JCCFzCFzCH=CHz C C lFa 19.4 g. (0.0650 mole) of CH3 CH3 HS'i0S iH CH2 H23H2 CH2 lFa CF3 and 250 ml. of 0.1 M solution of chloroplatinic acid inisopropyl alcohol was placed in an evacuated sealed glass ampule. Theampule was heated at C. for 72 hours while rocking end-to-end.Distillation of the reaction product gave clear viscous liquid, B.P. 183to 184 C. (2.15 mm), n 1.3875. Higher molecular weight polymer remainedas residue of the distillation.

EXAMPLE 8 The ultraviolet irradiation of an equirnolar mixture of CH2CH3 l. l, CHZ=CHCFZCFZCIJ COFzCFzCH=CHz and HslOs'lH N N CH3 CH2 t CF inthe presence of a catalytic amount of di-t-butylperoxide resulted in aviscous liquid product at end of 13 days.

A viscous liquid product was obtained from is cohydrolyzed with 25 molpercent (CH SiCl and 25 mol percent of C H SiCl in the presence ofwater, the following copolymer is obtained:

50 mol percent of 25 mol percent of (CH SiO units and 25 mol percent ofC H Si0 units.

9 EXAMPLE 10 When 50 mol percent of the triazine-containing silane usedin Example 9 is cohydrolyzed with 50 mol percent (CH SiCl a fluidcopolymer having the following composition is obtained:

50 mol percent of CH3 CHa 1, l. 1/2OS|1CH2CH2(C 1 92(1)(fiwlmzomomsioi/z CH2 N N H2 1 (IJH2 C CH2 O F3 (5112 C F3 (31% and 50mol percent (CH SiO units.

EXAMPLE 11 'When N Cl3SlCII2CH2(CFz)3C (fi(CF2)aCHzCHzSlCla N\ /N COFzCl is reacted with CH CHCH MgCI, the following composition isobtained Hydrolysis of this silane produces a siloxane which is readilyvulcanized.

That which is claimed is:

1. A compound of the formula 2,981,734 4/1961 Ratz et a1. 2602483,218,270 11/1965 Delman et a1. 260248 XR JOHN D. RANDOLPH, PrimaryExaminer I. M. FORD, Assistant Examiner U.S. Cl. X.R.

